Five new anilato-based, Ln(III)-containing, layered compounds have been prepared with the asymmetric ligand chlorocyananilato (C₆O₄(CN)Cl)²⁻; different Ln(III) ions Ce(III), Pr(III), Yb(III), and Dy(III); and the three different solvents H₂O, dimethylsolfoxide (DMSO), and dimethylformamide (DMF). Compounds [Ce₂(C₆O₄(CN)Cl)₃(DMF)₆]·2H₂O (1), [Pr₂(C₆O₄(CN)Cl)₃(DMF)₆] (2), [Pr₂(C₆O₄(CN)Cl)₃(DMSO)₆] (3), [Yb₂(C₆O₄(CN)Cl)₃(DMSO)₄]·2H₂O (4) and [H₃O][Dy(C₆O₄(CN)Cl)₂(H₂O)]·4H₂O (5) show the important role that the Ln(III) size, as well as the size and shape of the solvent may play in the crystal structure of each compound. Compounds 1–4 present (6,3)-2D hexagonal lattices, with important differences in the coordination number and geometry of the Ln(III) ion, as well as in the distortion of the hexagonal cavities, depending on the Ln(III) and solvent size. Compound 5 (the only one prepared with water) presents a (4,4)-2D square lattice, where the Dy(III) ions are surrounded by four chelating anilato ligands. Compounds 2–4 are essentially paramagnetic, confirming the presence of weak (if any) magnetic coupling mediated by the anilato ligands when connecting Ln(III) ions. Compounds 2–4 showed a red shift and a broadening of the emission band of the ligand. Compound 4 also showed a strong emission band attributed to the Yb(III), suggesting an antenna effect of the ligand. An energy transfer diagram is proposed to explain these luminescent properties.

Over the last 20 years, the use of metallic nanoparticles (MNPs) in catalysis has awakened a great interest in the scientific community, mainly due to the many advantages of this kind of nanostructures in catalytic applications. MNPs exhibit the characteristic stability of heterogeneous catalysts, but with a higher active surface area than conventional metallic materials. However, despite their higher activity, MNPs present a wide variety of active sites, which makes it difficult to control their selectivity in catalytic processes. An efficient way to modulate the activity/selectivity of MNPs is the use of coordinating ligands, which transforms the MNP surface, subsequently modifying the nanoparticle catalytic properties. In relation to this, the use of N-heterocyclic carbenes (NHC) as stabilizing ligands has demonstrated to be an effective tool to modify the size, stability, solubility and catalytic reactivity of MNPs. Although NHC-stabilized MNPs can be prepared by different synthetic methods, this review is centered on those prepared by an organometallic approach. Here, an organometallic precursor is decomposed under H₂ in the presence of non-stoichiometric amounts of the corresponding NHC-ligand. The resulting organometallic nanoparticles present a clean surface, which makes them perfect candidates for catalytic applications and surface studies. In short, this revision study emphasizes the great versatility of NHC ligands as MNP stabilizers, as well as their influence on catalysis.

We show the key role that the size and shape of the solvent molecules may play in the dimensionality and structure of a series of lanthanoid–chloranilato coordination polymers. We report the synthesis, structure and magnetic properties of six different coordination polymers prepared with Er(III) and chloranilato (C₆O₄Cl₂ ²⁻ = 3,6-dichloro-2,5-dihydroxy-1,4-benzoquinone) and six different solvents: [Er₂(C₆O₄Cl₂)₃(H₂O)₆]·10H₂O (1), [Er₂(C₆O₄Cl₂)₃(FMA)₆]·4FMA·2H₂O (2) (FMA = formamide = NH₂CHO), [Er₂(C₆O₄Cl₂)₃(DMSO)₄]·2DMSO·2H₂O (3) (DMSO = dimethy sulfoxide = Me₂SO), [Er₂(C₆O₄Cl₂)₃(DMF)₆] (4) (DMF = dimethylformamide = Me₂NCHO), [Er₂(C₆O₄Cl₂)₃(DMA)₄] (5) (DMA = dimethylacetamide = Me₂NC(Me)O) and [Er₂(C₆O₄Cl₂)₃(HMPA)(H₂O)₃]·H₂O (6) (HMPA = hexamethylphosphormamide = (Me₂N)₃PO). We show how the different solvent molecules modulate and determine important structural parameters such as the coordination number and geometry, the shape and distortions of the cavities, the presence of solvent molecules in these cavities, the interlayer space and even the dimensionality of the structure.

Mono and bimetallic platinum–ruthenium nanoparticles have been generated on N-doped graphene (NH₂-rGO) following an organometallic approach. Surface and structural studies confirmed the formation of bimetallic MNPs with controlled metal compositions. To evaluate the activity/selectivity of the different materials prepared we used the hydrogenation of acetophenone as a model reaction. We found that both the activity and selectivity of the supported-bimetallic NPs are highly dependent on the support and the atomic composition. The higher the Pt/Ru ratio, the higher the selectivity towards 1-phenylethanol. Indeed, a remarkable activity and selectivity in the hydrogenation of acetophenone was observed for Pt₅Ru₁@NH₂-rGO. The reactivity of these catalysts was also investigated in the hydrogenation of other substrates such as functionalized arenes (i.e. nitrobenzene and benzaldehyde) or hydroxymethylfurfural (HMF), demonstrating that it is possible to control the activity and selectivity of bimetallic Pt–Ru MNPs supported on N-doped graphene by adjusting their metal composition.

Reducing CO₂ to CO via the reverse water–gas shift (RWGS) reaction is a promising strategy for carbon capture and utilization (CCU). In this study, tailored magnetic catalysts were designed through the pyrolysis of a Co-based MOF to form well-defined nanoparticles. As a result, carbon-encapsulated cobalt nanoparticles (Co@C) and palladium-doped cobalt nanoparticles (CoPd/Co@C) were synthesized and thoroughly characterized using a variety of techniques, including in situ X-ray absorption and diffraction experiments. These carbon-based catalysts were simultaneously used as heating agents and catalysts for the magnetically induced RWGS reaction, exhibiting remarkable activity and selectivity for syngas production. CO₂ conversions of 61.1% and 71.1% were obtained for Co@C and CoPd/Co@C (63 mT, 2 kW, 320 kHz), respectively. Using magnetic induction heating (MIH), these catalysts operate at lower local temperatures and with greater energy efficiency than conventional thermal heating, while achieving superior CO production efficiency. Notably, CoPd/Co@C achieved highly satisfactory CO production efficiency (478.5 mL_CO/kW·h), demonstrating a significant improvement compared to the analogous process utilizing magnetically induced heating. Furthermore, CoPd/Co@C exhibited unwavering stability, maintaining its performance for more than 200 h without significant degradation or need for reactivation. This study highlights the potential of MIH for industrial applications in CO₂ reduction, offering a more renewable and economically viable alternative to traditional methods.